Azido-s-triazines

ABSTRACT

Method of combating insects comprising the use of s-triazine derivatives of the formula   WHEREIN R1 represents hydrogen, cyclopropyl, 1methylcyclopropyl, 2-methylcyclopropyl, C1-C5 alkyl, C3-C4 alkenyl, C3-C4 alkynyl, or C1-C5 alkyl substituted by cyano and n represents 0 or 1.

United States Patent Herzog et al.

1111 3,853,868 1451 Dec. .10, 1974 AZIDO-S-TRIAZINES [75] Inventors:Alexis Herzog; Hans Ulrich Brechbuehler, both of Basel, Switzerland [73]Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: May 12, 1972 [21] Appl. No.: 252,729

[30] Foreign Application Priority Data June 1, 1971 Switzerland 7925/71Apr. 10, 1972 Switzerland 5214/72 [52] U.S. CL... 260/249.6, 424/249[51] Int. Cl C07d 55/22 [58] Field of Search 260/249.6

[56] References Cited UNITED STATES PATENTS 3,238,230 3/1966 Haszeldineet a1 260/349 3,497,511 2/1970 Schwarze et al 260/249.6 X

6/1971 Berrer et al.... 260/249.6 1/1972 Schwarze 260/249.6 X

Primary Examiner.lohn M. Ford Attorney, Agent, or Firml-larry Falber;Frederick H.

Rabin [5 7] ABSTRACT Method of combating insects comprising the use ofstriazine derivatives of the formula 3 Claims, No Drawings wherein'AZIDO-S-TRIAZINES The present invention relates to a method ofcombating insects which comprises the use of s-triazine derivatives ofthe formula 3 n v f w l NYN formula 3 n E K W Z wherein R representscyclopropyl, 2-methylcyclopropyl, methyl, ethyl, n-propyl, isopropyl,n-, i-, sec.- and tert.butyl, l-cyanoethyl, l-cyanopropyl, and nrepresents or 1.

The following compounds may be cited as examples of suitable compoundsof the formula 1]:

Compound mp: C 7

4-azido-2-methylamino-6- cyclopropylamino-s-triazine4-azido-2-ethylamino-6- cyclopropylamino-s-triazine 4-azidoLisopropylamino-- cyclopropylamino-s-triazine 4-azido-2-sec.butylamino-6- cyclopropylamino-s-triazine 4-azido-2-tert. butylamino-6-cyclopropylamino-s-triazine4-azido-2.6-bis-cyclopropylamino-s-triazine 4-azido-2-isobutylamino-6-cyclop ropylamino-s-triazine 4-azido-2-(2'-cyanobut-2'- ylamino)-6-cyclopropylaminos-triazine 4-azido-2-(3'-cyanopent-3'-ylamino)-6-cyclopropylaminos-triazine 4-azido-2-( l '-cyanoethylamino)-6-cyclopropylaminos-triazine 4-azido-2-( l '-cyanoprop l ylamino)-6-cyclopropylaminoll2-ll4 Continued Compound mp: C

s-triazine 7880 4-azido-2-ethylamino-6-(2'-methylcyclopropylamino)-striazine 98-l024-azido-2-amino-G-cyclopropylamino-s-triazine l3 l-l 32,54-azido-2-allylamino-G-cyclopropylamino-s-triazine 56,5-58.5

4-azido2-propargylaminc-6- cyclopropylamino-s-triazine The inventionalso relates to new compounds, process for their manufacture and topesticidal agents which contain these compounds as active substance.

The new compounds have the formula wn pw wm wherein R representshydrogen, C -C alkenyl or C -C alkynyl and n represents 0 or 1.

Preferred C C alkenyl or C -C alkynyl radicals for R arethe allyl andpropargyl radicals.

The compounds of the formula I are manufactured by reacting achloro-bis-amino-s-triazine of the formula C1 (IV) wherein n and R havethe meanings given for the formula l, with an alkali metal azide in thepresence of a base, or by reacting the compound of the fonnula IV withhydrazine and reacting the resulting hydrazino-striazine of the formulaI (011 -mrkN)mm I wherein n and R have the meanings given for theformula l, with nitrous acid or an alkali metal nitrite, or by reactingthe compound of the formula CH -liP'GH wherein R and n have the meaninggiven for the formula I and Y represents an inorganic or organic acidradical, in particular chlorine, bromine or iodine, with an alkali metalazide.

Suitable bases are in particular tertiary amines, such as trialkylamines, also hydroxides, oxides and carbonates of alkali and alkalineearth metals. Water is used preferably as solvent or diluent for thereactions; but it is also possible to use organic solvents which aremiscible with water, such as ketones, ethers and ether-like compounds,nitriles, N,N-disubstituted amides, sulphoxides etc., also solventswhich are immiscible with water, for example aliphatic and aromatichydrocarbons and halogenated hydrocarbons.

Analogous compounds are described in Belgian Patent No. 730 133 as totalherbicides and selective herbicides.

Analogous compounds are also described as herbicides in French PatentNo. 1537.3 1 2, and attention is drawn to their possible insecticidalaction.

In comparison to these active substances, the compounds of the formula Idisplay a distinct superiority in the fly test.

It is a commonly known fact that phosphoric acid esters, asrepresentatives of classical insecticides, kill both vertebrates andinvertebrates by cholinesterase inhibition through the accumulation ofacetyl choline at the nerve endings. The accumulated acetyl cholineseverely disrupts the function of the nervous system and death occurs asa consequence after a few hours. In contrast to the classicalinsecticides, which, in the form of contact or ingest poisons, kill orparalyse the insects in a few hours, the active substances of theformula I primarily influence the terminal phase of the larvaldevelopment. Depending on the time of application, the development isarrested in the larval or pupal stage. This mode of action is notcomparable with that of classical insecticides, chemosterilants orjuvenile hormones.

The active substances of the formula I can be used chiefly for combatingthe following storage and hygiene pests:

Blattidae Kelotermitidae Carabidae Elateridae Tenebrionidae DermestidaeCucujidae Scarabaeidae Culicidae Simuliidae Tipuliclae MuscidaeCalliphoridae Orthoptera lsoptera Coleoptera Diptera The compounds ofthe formula I can be used as pure concentrate or together with suitablecarriers and/or additives. Suitable carriers and additives can be solidor liquid and correspond to the substance conventionally used informulation technique such, for example, as solvents, dispersants,wetting agents, adhesives, thickeners, binders and/or fertilisers.

The agents according to the invention are manufactured in known mannerby intimately mixing and/or grinding active substances of the formula Iwith the suitable carriers, optionally with the addition of dispersantsor solvents which are inert towards the active substances. The activesubstances may be available and can be used in the following forms:

Solid forms:

dusts, tracking agents, granules, coated granules, impregnated granulesand homogeneous granules, premix (feed additive).

Liquid forms:

a. active substances which are dispersible in water: wettable powders,pastes, emulsions;

b. solutions: aerosols.

To manufacture solid forms (dusts, tracking agents), the activesubstances are mixed with solid carriers. Suitable carriers are, 'forexample: kaolin, talcum, bolus, loess, chalk, limestone, groundlimestone. attacluy. dolomite, diatomaceous earth, precipitated silica.alkaline earth silicates, sodium and potassium aluminum silicates(feldspar and mica), secondary calcium phosphate, calcium and magnesiumsulphates, magnesium oxide, ground synthetic materials, fertilisers, forexam ple ammonium sulphate, ammonium phosphate, am monium nitrate, urea,ground vegetable products, such as corn meal, bark dust, sawdust,nutshell meal, cellulose powder, residues of plant extractions,activated charcoal etc. These substances can either be used alone or inadmixture with one another.

Granules can be very easily manufactured by dissolving an activesubstance of the formula I in an organic solvent and applying theresulting solution to a granulated material. for example attapulgite,SiO granicalcium, bentonite etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the activesubstances of the formula I with polymerisable compounds(urea/formaldehyde; dicyandiamide/ formaldehyde; melamine/formaldehydeor others), whereupon a mild polymerisation is carried out that does notaffect the active substances and in theprocess of which the granulationis carried out during the gel formation. It is more advantageous toimpregnate finished, porous polymer granules (urea/formaldehyde,polyacrylonitrile, polyesters or others) which have a specific surfacearea and a favourable predeterminablc adsorption/desorption ratio, withthe active substances. for example in the form oftheir solutions (in alow boiling solvent) and to remove the solvent. Polymer gran ules ofthis kind in the form of microgranules having a bulk density of 300g/litre to 600 g/litre can also be manufactured with the aid ofatomisers. The dusting can be carried out from aircraft.

It is also possible to obtain granules by compacting the carrier withthe active substance and carriers and subsequently comminuting theproduct.

To these mixtures can also be added additives which stabilize the activesubstance and/or non-ionic, anionic and cationic surface activesubstances, which for example improve the adhesion of the activeingredients on plants or parts of plants (adhesives and agglutinants)and/or ensure a better wettability (wetting agents) and dispersibility(dispersing agents). The following substances, for example, aresuitable: olein/chalk mixture. cellulose derivatives (methyl cellulose,carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl anddialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and8 to 9 carbon atoms in the alkyl radical, lignin sulfonic acids. theiralkali metal and alkaline earth metal salts, polyethylene glycol ethers(can bowaxes), fatty alcohol polyethylene glycol ethers having 5 to 20ethylene oxide radicals per molecule and 8 to 18 carbon atoms in thefatty alcohol moiety, condensation products of ethylene oxide/propyleneoxide, polyvinyl pyrrolidones, polyvinylalcohols, condensation productsof urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e.,wettable powders, pastes and emulsifiable concentrates, are agents whichcan be diluted with water to any concentration desired. They consist ofactive substance, carrier, optionally additives which stabilize theactive substance, surface-active substances and anti-foam agents and,optionally, solvents.

Wettable powders and pastes are obtained by mixing and grinding theactive substances with dispersing agents and pulverulent carriers insuitable apparatus until homogeneity is attained. Carriers are, forexample, those mentioned for the solid forms of application. In manycases it is advantageous to use mixtures of different carriers. Asdispersing agents there can be used, for example, condensation productsof sulfonated naphthalene and sulfonated naphthalene derivatives withformaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, as well as alkali, ammoniumand alkaline earth metal salts of lignin sulfonic acid, in addition,alkylaryl sulfonates, alkali and alkaline earth metal salts of dibutylnaphthalene sulfonic acid, fatty alcohol sulfates such as salts ofsulfated hexadecanols, heptadecanols, octadecanols, and salts ofsulfated fatty alcohol glycol ethers, the sodium salt of oleoylethionate, the sodium salt of oleoyl methyl tauride, ditertiaryacetylene glycols, dialkyl dilauryl ammonium chloride and fatty acidalkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

The active substances are so mixed, ground, sieved and strained with theadditives mentioned above that, in wettable powders, the solid particlesize of from 0.02 to 0.04 and in pastes, of 0.03 is not exceeded. Toproduce emulsifiable concentrates and pastes, dispersing agents such asthose given in the previous paragraphs, organic solvents and water areused. Examples of suitable solvents are the following: alcohols,benzene, xylenes, toluene, dimethyl sulfoxide, and mineral oil fractionsboiling between 120 and 350C. The solvents must be practicallyodourless, not phytotoxic, inert to the active substances and notreadily inflammable.

Furthermore, the agents according to the invention can be applied in theform of solutions. For this purpose the active substance or severalactive substances of general formula I are dissolved in suitable organicsolvents, mixtures of solvents or in water. Aliphatic and aromatichydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, andmineral oils alone or mixed with each other, can be used as organicsolvents.

The content of active substance in the above described agents is between0.1 to 95%, in which connection it should be mentioned that in the caseof application from aircraft or some other suitable means ofapplication, it is possible to use concentrations of up to 99.5% or evenpure active substance.

The active substances of the formula I can, for example, be formulatedas follows: Dusts The following substances are used to manufacture (a) a5% and (b) a 2% dust:

a. 0.5 parts of active substance 99.5 parts of talcum b. 2 parts ofactive substance 1 part of highly disperse silica 97 parts of talcum.

The active substances are mixed with the carriers and ground. Trackingagent 5 parts of active substance are mixed with parts of carbonate oflime and the mixture is ground to an average particle size of 80,u..Granules 5 parts of active substance are dissolved in a solvent, e.g.methylene chloride, and the solution is mixed with 2 parts ofpolyethylene glycol (Carbowax).

91.5 parts of calcium carbonate are impregnated with the mixture and 1.5parts of precipitated silica are admixed and the solvent is subsequentlyevaporated. Bait granules 2.0 parts of active substance 0.05 parts ofcolouring matter 1.0 part of celite or China clay are mixed and finelyground. The granules are then mixed with 96.8 parts of crystallisedsugar and impregnated with 0.1 part of an adhesive dissolved, forexample, in a small amount of isopropanol, and the solvent isevaporated. Wettable powder 50 parts of active substance 5 parts of adispersing agent, for example sodium lignin sulphonate,

5 parts of a wetting agent, dibutylnaphthalenesulphonic acid 10 parts ofsilica and 30 parts of China clay are mixed and the mixture is finelyground. Emulsifiable concentrate 20 parts of active substance 20 partsof an emulsifying agent, for example a mixture of alkylarylpolyglycolether and alkylarylsulphonates, and 60 parts of a solvent, for examplexylene, are mixed until the solution is completely homogeneous. Thisconcentrate can be diluted with water to give emulsions of every desiredconcentration. Premix (feed additive) 0.25 part of active substance andfor example 4.75 parts of secondary calcium phosphate, or China clay,aerosil or carbonate of lime, are homogeneously mixed with 95.00 partsof a feed, e.g. rabbit feed. Aerosol In an aerosol filling plant 0.25part of active substance 25.00 parts of 1,1,l-trichloroethane and 24.75parts of benzene are filled into aerosol containers with 50.00 parts ofpower gas consisting of freon 1 H12 in the ratio 1:1. Sprays Thefollowing constituents are used to manufacture (a) a 50% and (b) a 2%spray: a. 5 parts of active substance 1 part of epichlorohydrin 94 partsof petroleum ether (boiling limitsz16- 0l90C). b. 2 parts of activesubstance 1 part of diazinone 97 parts of kerosene. The agents hereindescribed can be mixed with other biocidal active substances or agents.In addition to the cited compounds of the formula I, the new agents maycontain, for example, insecticides, fungicides, bactericides,fungistatic agents, bacteriostatic agents, in order to broaden theactivity spectrum.

The active substances of the formula I are applicable as developmentretardants for combating insects. In contrast to classical insecticides,which, in the form of contact or ingest poisons, kill or paralyse theinsects in a few hours, the active substances of the formula I primarilyinfluence the larval development. The activity consists in adevitalisation of the egg larvae or in preventing adult insects fromhatching from pupae. This activity is not comparable with that ofclassical insecticides, chemosterilants or juvenile hormones.

Since the active substances of the formula I are not harmful towarm-blooded animals, new horizons are opened up for the pricipal fieldof application: that of combating maggot flies. Instead of as in thecase of insecticides treating large areas, it is possible to administerthe active substances of the formula l to farm animals, for examplehens, with the feed. The active substances pass through the alimentarytract unimpaired and are present in the eliminated faeces. The

fresh excrement is an ideal breeding ground for hygiene pests, such asflies. The larvae which hatch from the eggs come into immediate contactwith the new active substance and their subsequent development ishindered The larger maggots which migrate from old to fresh excrementlikewise come in contact with the active substances and their terminalphase is impaired. The maggots pupate without any noteworthy mortality,but no flies emerge from the pupae.

Besides the selective arrest of development in insects, the applicationvia feed may be highlighted on account of the non-harmful environmentalaspect, since only the excrement contains the active substances.

The agents, or the active substances contained therein, unfold theirdevelopment retardant action primarily therefore on the larval stages ofinsects, preferably of the order Diptera. They are also applicable forstorage protection, in particular for the protection of foodstuffs andsupplies in which insect larvae, for example of the order Coleoptera,normally develop.

EXAMPLE 1 After thoroughly mixing the treated substrate, the solvent isevaporated. Then 2 X 25 one day old Musca domestica maggots aredeposited per active substance. The pupae are washed out after 5 daysand their hatching rate determined after 10 days. An eventual influenceon the metamorphosis is thus ascertained.

Result Active Substance n Pupae n Flies -azido-2rnethylamino-f-cyclopropylamino-s-triazine 35 t) 4-azldo-2-ethylamino-6cyclopropylamino-s-triazine 34 [I 4-azid0-2-isopropylamino-ocyclopropylaminostriazine 39 t) 4-azido-2 sec. butylamino-6cyclopropylaminos-triazine 23' t)4-azido-2.6-bis-cyclopropylaminos-triazine 43 U4-azido-2-isobutylamino--cyclopropylamino-striazine 5t) 0 4azido-2{ l-cyanoethylamino ResuleContinued Active Substance n Pupae n Flies6-cyclopropylaminos-triazine H) U 7 Control 49 4b We claim:

1. A compound of the formula (CH E -l-H\'-f W NHR l I N N wherein Rrepresents hydrogen, C C. alkenyl or C C alkynyl and n represents 0 or1.

2. 4azido-2-allylamino-6-cyclopropylamino-striazine.

3. 4-azido-2-propargylamino-6-cyclopropylamino-striazine.

1. A COMPOUND OF THE FORMULA 2.4-azido-2-allylamino-6-cyclopropylamino-s-triazine. 3.4-azido-2-propargylamino-6-cyclopropylamino-s-triazine.